CN113424349A - Secondary battery - Google Patents

Secondary battery Download PDF

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Publication number
CN113424349A
CN113424349A CN202080010602.9A CN202080010602A CN113424349A CN 113424349 A CN113424349 A CN 113424349A CN 202080010602 A CN202080010602 A CN 202080010602A CN 113424349 A CN113424349 A CN 113424349A
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Prior art keywords
layer
electrode
secondary battery
oxide semiconductor
peak
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津国和之
小笠原树里
殿川孝司
加藤宽之
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Micronics Japan Co Ltd
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Micronics Japan Co Ltd
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Abstract

A secondary battery having improved performance. According to the present embodiment, a secondary battery (100) includes a first electrode (21), a second electrode (22), a first layer (11) disposed on the first electrode (21) and including a first n-type oxide semiconductor, a second layer (12) disposed on the first layer (11) and including a second n-type oxide semiconductor material and a first insulating material, a third layer (13) disposed on the second layer (12) and being a solid electrolyte layer, and a second layer (13) disposed on the third layer (13) and including hexagonal Ni (OH)2A fourth layer (14) of microcrystals.

Description

Secondary battery
Technical Field
The present disclosure relates to a technique for improving the performance of a secondary battery.
Background
Patent document 1 discloses a secondary battery including a first oxide semiconductor layer, a first charging layer, a second charging layer, a hydroxide layer, and a third oxide semiconductor layer between a first electrode and a second electrode. The third oxide semiconductor layer is nickel oxide (NiO), and the hydroxide layer is nickel hydroxide (Ni (OH)2). The nickel hydroxide layer is formed by an electrical stimulation step of performing electrical treatment after forming the second electrode. That is, by applying a pulse voltage between the first electrode and the second electrode, a nickel hydroxide layer is formed between the second charging layer and the third oxide semiconductor layer.
Patent document 2 discloses a secondary battery including a first oxide semiconductor layer, a first charging layer, a second charging layer, and a third oxide semiconductor layer between a first electrode and a second electrode. The third oxide semiconductor layer is a p-type oxide semiconductor layer with the thickness of 200nm-1000 nm. Specifically, the third oxide semiconductor layer is a p-type oxide semiconductor layer including nickel oxide NiO and nickel hydroxide (Ni (OH))2) The mixed layer of (1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-37261;
patent document 2: japanese patent laid-open publication No. 2018-152311.
Disclosure of Invention
Problems to be solved by the invention
In such a secondary battery, further improvement in performance is desired.
An object of the present disclosure is to improve the performance of a secondary battery.
Means for solving the problems
An example aspect of the embodiments is a secondary battery including: a first electrode; a second electrode; a first layer disposed between the first and second electrodes and comprising a first n-type oxide semiconductor material; a second layer disposed on the first layer and including a second n-type oxide semiconductor material and a first insulating material; a third layer that is provided on the second layer and is a solid electrolyte layer; and a fourth layer disposed on the third layer and comprising hexagonal Ni (OH)2And (4) microcrystals.
In the above-described secondary battery, in an X-ray diffraction pattern obtained by performing X-ray diffraction measurement by grazing incidence X-ray diffraction method on the fourth layer, there may be ni (oh) showing2The first peak of diffraction intensity of (001) plane of (2) and shows Ni (OH)2A second peak of the diffraction intensity of the (100) plane of (c).
According to another exemplary aspect of the embodiments, a secondary battery includes: a first electrode; a second electrode; a first layer disposed between the first and second electrodes and comprising a first n-type oxide semiconductor material; a second layer disposed on the first layer and including a second n-type oxide semiconductor material and a first insulating material; a third layer that is provided on the second layer and is a solid electrolyte layer; and a fourth layer disposed on the third layer and comprising crystallites of nickel hydroxide. In an X-ray diffraction pattern obtained by performing X-ray diffraction measurement by grazing incidence X-ray diffraction method on the fourth layer, there are a first peak showing the diffraction intensity of the (001) plane of nickel hydroxide and Ni (OH)2A second peak of the diffraction intensity of the (100) plane of (c).
In the above secondary battery, the full width at half maximum of the first peak is preferably larger than the full width at half maximum of the second peak.
In the above secondary battery, the planar size of the microcrystals is preferably 200nm or less.
In the above secondary battery, the fourth layer may be in contact with the second electrode.
In the above secondary battery, the thickness of the fourth layer may be 500nm or more.
Advantageous effects of the invention
According to the present disclosure, a technique of improving the performance of a secondary battery may be provided.
Drawings
Fig. 1 schematically shows a laminated structure of a secondary battery according to a first embodiment;
FIG. 2 shows a surface SEM of a fourth layer;
FIG. 3 shows a surface SEM of a fourth layer;
FIG. 4 shows a surface SEM of a fourth layer;
FIG. 5 shows a surface SEM of a fourth layer;
FIG. 6 shows a cross-sectional SEM of a fourth layer;
FIG. 7 shows an X-ray diffraction pattern of a fourth layer;
FIG. 8 schematically shows Ni (OH)2The crystal structure of (a);
fig. 9 is a flowchart showing a method of manufacturing a secondary battery; and
fig. 10 shows a cross-sectional SEM photograph of the fourth layer.
Detailed Description
Examples of embodiments of the present disclosure will be described below with reference to the accompanying drawings. The following description shows preferred embodiments of the present disclosure, and the technical scope of the present disclosure is not limited to the following embodiments.
[ first embodiment ]
(laminated Structure of Secondary Battery)
The basic structure of the secondary battery according to the present embodiment will be described below with reference to fig. 1. Fig. 1 is a sectional view schematically showing the laminated structure of a secondary battery 100.
In fig. 1, the secondary battery 100 has a laminated structure in which a first electrode 21, a first layer 11, a second layer 12, a third layer 13, a fourth layer 14, and a second electrode 22 are laminated in this order.
[ first electrode 21]
The first electrode 21 serves as a negative electrode of the secondary battery 100. The first electrode 21 is a conductive sheet or a conductive substrate serving as a base material. For example, a metal foil sheet such as a SUS sheet or an aluminum sheet can be used as the first electrode 21. Note that it is also possible to prepare a base material formed of an insulator and form the first electrode 21 on the substrate. When the first electrode 21 is formed on an insulating base material, a metal material such as tungsten (W), chromium (Cr), or titanium (Ti) can be used as a material of the first electrode 21. As a material of the first electrode 21, an alloy film including aluminum (Al), silver (Ag), or the like can be used. When the first electrode 21 is formed on the substrate, the first electrode 21 can be formed in the same manner as the second electrode 22 described later.
[ first layer 11]
The first layer 11 is disposed on the first electrode 21. The first layer 11 is provided on the first electrode 21 on the second electrode 22 side. The first layer 11 is formed in contact with the first electrode 21. The thickness of the first layer 11 is, for example, about 50nm to 200 nm.
The first layer 11 includes an n-type oxide semiconductor material (first n-type oxide semiconductor material). The first layer 11 is an n-type oxide semiconductor layer formed with a predetermined thickness. It is possible to use, for example, titanium dioxide (TiO)2) Tin oxide (SnO)2) Or zinc oxide (ZnO) as the first layer 11. The first layer 11 is, for example, an n-type oxide semiconductor layer formed on the first electrode 21 by sputtering, vapor deposition, or the like. Particular preference is given to using titanium dioxide (TiO)2) As the material of the first layer 11.
[ second layer 12]
A second layer 12 serving as a negative electrode active material is provided on the first layer 11. The second layer 12 is provided on the first layer 11 on the second electrode 22 side. The second layer 12 is formed in contact with the first layer 11. The thickness of the second layer 12 is, for example, 200nm to 3000 nm. The thickness of the second layer 12 may be, for example, 10 μm or more.
The second layer 12 includes an insulating material (first insulating material). A silicone resin can be used as the first insulating material. For example, it is preferable to use a silicon compound having a main skeleton bonded by siloxane such as silicon oxide: (Silicone) as the first insulating material. Thus, the second layer 12 comprises silicon oxide (SiO) as the first insulating materialx)。
The second layer 12 includes an n-type oxide semiconductor material (second n-type oxide semiconductor material) in addition to an insulating material (first insulating material). That is, the second layer 12 is formed of a mixture of the first insulating material and the second n-type oxide semiconductor material. For example, a fine-grained n-type oxide semiconductor can be used as the second n-type oxide semiconductor material.
For example, the second layer 12 is formed of silicon oxide and titanium oxide, with a second n-type oxide semiconductor material serving as titanium oxide. In addition, as an n-type oxide semiconductor material that can be used for the second layer 12, tin oxide (SnO)2) Zinc oxide (ZnO) and magnesium oxide (MgO) are preferred. Combinations of two, three, or all of titanium oxide, tin oxide, zinc oxide, and magnesium oxide may also be used.
The second n-type oxide semiconductor material contained in the second layer 12 and the first n-type oxide semiconductor material contained in the first layer 11 may be the same or different. For example, when the first n-type oxide semiconductor material contained in the first layer 11 is titanium oxide, the second n-type oxide semiconductor material of the second layer 12 may be titanium oxide or an n-type oxide semiconductor material other than titanium oxide.
[ third layer 13]
A third layer 13 serving as a solid electrolyte is provided on the second layer 12. The third layer 13 is provided on the second layer 12 on the second electrode 22 side. The third layer 13 is formed in contact with the second layer 12. The thickness of the third layer 13 is preferably 50nm or more and 800nm or less. The thickness of the third layer 13 may be 800nm or more.
Third layer 13 Conditioning H+And electron (e)-) The movement of (2). The third layer 13 is a layer containing tantalum oxide. For example, the third layer 13 can be formed of a tantalum oxide film (TaO) having a predetermined thicknessxFilm) is formed. Specifically, the third layer 13 is TaO formed on the second layer 12 by sputtering or the likexAnd (3) a layer. The third layer 13 is preferably an amorphous layer comprising tantalum oxide. Alternatively, the third layer 13 preferably comprises a plurality of oxidationsA nanoparticle layer of tantalum nanoparticles.
[ fourth layer 14]
A fourth layer 14 serving as a positive electrode active material layer or a solid electrolyte layer is provided on the third layer 13. The fourth layer 14 is provided on the third layer 13 on the second electrode 22 side. The fourth layer 14 is formed in contact with the third layer 13. The fourth layer 14 comprises nickel hydroxide (Ni (OH)2). Specifically, a nickel hydroxide layer formed in a predetermined thickness becomes the fourth layer 14. The thickness of the fourth layer 14 is preferably 500nm or more. The thickness of the fourth layer 14 is preferably 3600nm or less.
The fourth layer 14 comprises Ni (OH)2A plurality of hexagonal crystallites. The fourth layer 14 is a layer in which Ni (OH) is laminated2An assembly of crystallites. For example, Ni (OH)2The crystallite has a planar size of 200nm or less. The fourth layer 14 may be formed by, for example, a pull-out method or a convection self-assembly method. In addition, a metal material such as cobalt (Co) or zinc (Zn) may be added to the nickel hydroxide layer of the fourth layer 14 to improve the performance.
[ second electrode 22]
The second electrode 22 is disposed on the fourth layer 14. The second electrode 22 is formed in contact with the fourth layer 14. The second electrode 22 may be formed of a conductive film. A metal material such as chromium (Cr) or copper (Cu) may be used as the material of the second electrode 22. An alloy film including aluminum (Al), silver (Ag), or the like may also be used as the material of the second electrode 22. Examples of the method of forming the alloy film include vapor film deposition methods such as sputtering, ion plating, electron beam vapor deposition, vacuum deposition, and chemical vapor deposition. The metal electrode can be formed by electrolytic plating, electroless plating, or the like. As the metal used for the plating process, copper alloy, nickel, silver, gold, zinc, tin, or the like can be generally used. For example, the second electrode 22 is an Al film having a thickness of 300 nm.
A nickel hydroxide film is directly formed on the third layer 13 as a solid electrolyte layer, thereby forming a fourth layer 14. By doing so, the fourth layer 14 can be formed as a nickel hydroxide layer having a sufficient thickness. Therefore, the storage capacity can be increased by adding the positive electrode active material. Further, by forming a film deposited with Ni (OH)2The structure of the microcrystal can be easily realizedThe metal material is added.
On the other hand, in patent document 1, the second electrode is formed by an electrical stimulation step of performing electrical treatment after the second electrode is formed. Therefore, Ni (OH) cannot be formed2And (4) microcrystals. In addition, it is difficult to form a nickel hydroxide layer having a sufficient thickness.
In patent document 2, a nickel oxide film containing hydrogen is formed by a sputtering deposition method. Specifically, Ni or NiO is used as the target. Water is drawn from water vapor or moisture in the chamber of the sputter deposition apparatus. Therefore, Ni (OH) cannot be formed2And (4) microcrystals. In addition, it is difficult to form a nickel hydroxide layer having a sufficient thickness.
Fig. 2 and 3 show surface SEM (scanning electron microscope) photographs of the fourth layer 14. In fig. 3, the magnification is larger than that of fig. 2. As can be seen from fig. 2 and 3, the planar size of the crystallites is 200nm or less. The planar size of the crystallites can be determined from surface SEM photographs.
Fig. 4 is a surface SEM photograph of the fourth layer 14, and fig. 5 is a cross-sectional SEM photograph. The fourth layer 14 is an aggregate of microcrystals having a planar size of about 100nm and a thickness of about several tens of nm.
Fig. 6 shows an SEM photograph of a 3600nm thick nickel hydroxide layer over a wide range, i.e. a cross-sectional SEM photograph at low magnification. As described above, even if the film thickness is 3600nm, the nickel hydroxide layer having a microcrystalline structure can be uniformly formed.
Fig. 7 shows an X-ray diffraction pattern (spectrum) of the exposed fourth layer 14. In fig. 7, the horizontal axis represents the diffraction angle 2 θ (angle between the incident X-ray direction and the diffracted X-ray direction), and the vertical axis represents the diffraction intensity (a.u). In this example, X-ray diffraction measurement was performed by grazing incidence X-ray diffraction method using CuK α rays each having a wavelength of 1.5418 angstroms.
Three peaks a to C appear in the X-ray diffraction pattern of the fourth layer 14. Peak A corresponds to Ni (OH)2(001) plane of (a). Peak B corresponds to Ni (OH)2The (100) plane of (1). The peak C is caused by silicon (Si) contained in the third layer 13 below the fourth layer 14. Ni (OH)2Exists by performing a pass on the fourth layer 14An X-ray diffraction pattern obtained by X-ray diffraction measurement by grazing incidence X-ray diffraction method. In addition, in the X-ray diffraction pattern, Ni (OH) is present2Peak of diffraction angle of (100) plane (2). (001) The peak of the plane is larger than the peak of the (100) plane. (001) The full width at half maximum of the peak of the plane is greater than the full width at half maximum of the peak of the (100) plane.
Ni(OH)2Will be described with reference to fig. 8. Ni (OH)2Has a hexagonal crystal structure as shown in fig. 8. The hexagonal crystal plane is called the (001) plane and the square crystal plane is called the (100) plane. Ni (OH)2Has a hexagonal crystal structure and a c-axis lattice constant of about 4.6 angstroms. (001) The X-ray diffraction peak corresponding to the plane is 19.581 °. (100) The X-ray diffraction peak corresponding to the plane was 33.40 °. It is inferred from the X-ray diffraction pattern and the surface SEM photograph that the crystal is a thin hexagonal planar crystallite in the c-axis direction.
Capable of depositing Ni (OH) having such a crystal structure2As the fourth layer 14 to improve cell performance. That is, by forming the fourth layer 14 having the above-described crystal structure on the third layer 13 serving as the solid electrolyte layer, the battery performance can be improved. For example, the storage capacity can be increased by adding a positive electrode active material layer. Further, since the fourth layer 14 can be formed without using the electrical stimulation step, malfunction caused by electrical stimulation can be reduced.
(production method)
Next, a method of manufacturing the secondary battery 100 according to the present embodiment will be described with reference to fig. 9. Fig. 9 is a flowchart illustrating a method of manufacturing the secondary battery 100.
First, the first layer 11 is formed on the first electrode 21 (S11). The first layer 11 includes the first n-type oxide semiconductor material as described above. For example, in the first layer 11, by sputtering using Ti or TiO as a target, TiO can be formed2The film serves as the first layer 11. The first layer 11 can be TiO with a thickness of 50nm to 200nm2A film. The first electrode 21 is, for example, a tungsten electrode.
Next, the second layer 12 is formed on the first layer 11 (S12). The second layer 12 can be formed by pyrolysis of the coating. First, a coating liquid is prepared by mixing a solvent with a mixture of a precursor of titanium oxide, tin oxide, or zinc oxide and silicone oil. An example in which the second layer 12 is formed of silicon oxide as a first insulating material and titanium oxide as a second n-type oxide insulating material will be described. In this case, a fatty acid titanium can be used as a precursor of titanium oxide. The fatty acid titanium and the silicone oil were stirred together with the solvent to prepare a coating liquid.
The coating liquid is applied onto the first layer 11 by spin coating, slit coating, or the like. Specifically, the coating liquid was applied by a spin coating apparatus at a spin speed of 500 to 3000 rpm.
Then, the coating film is dried, baked, and irradiated with ultraviolet light, whereby the second layer 12 can be formed on the first layer 11. For example, the workpiece is dried on a hot plate after the application of the coating liquid. The drying temperature on the hot plate is about 30 ℃ to 200 ℃ and the drying time is about 5 minutes to 30 minutes. After the workpiece is dried, the workpiece is baked in the atmosphere using a baking oven. The baking temperature is, for example, about 300 ℃ to 600 ℃ and the baking time is about 10 minutes to 60 minutes.
Thereby, the fatty acid salt is decomposed to form a titanium dioxide fine particle layer covered with a silicone insulating film. Specifically, the fine particle layer has a structure in which a metal salt of titanium dioxide coated with silicone is buried in the silicone layer. The baked coating film was irradiated with ultraviolet light using a low-pressure mercury lamp. The ultraviolet irradiation time is 10 to 60 minutes.
For example, when the second n-type oxide semiconductor is titanium oxide, titanium stearate can be used as another example of the precursor. Titanium oxide, tin oxide, and zinc oxide are formed by decomposing fatty acid salts which are precursors of metal oxides. For titanium oxide, tin oxide, zinc oxide, or the like, fine particles of an oxide semiconductor can also be used without using a precursor. Nanoparticles of titanium oxide or zinc oxide are mixed with silicone oil to make a mixture. Further, a solvent is mixed with the mixture to prepare a coating liquid.
The third layer 13 is formed on the second layer 12 (S13). The third layer 13 comprises tantalum oxide as described above. For example, Ta or Ta can be used2O5Sputtering as a target to form a third layer13. Alternatively, instead of the sputtering deposition, a film formation method such as vapor deposition or ion plating can be used. By using these film forming methods, TaO can be formedxThe film serves as the third layer 13. In the sputter deposition, only argon (Ar) gas may be used, or oxygen (O) may be used2) Gas was added to argon and then supplied. The third layer 13 may be TaO having a thickness of 50nm or more and 800nm or lessxAnd (3) a membrane. Here, as the third layer 13, amorphous TaO is preferably formedxFilm or TaO having a plurality of tantalum oxide nanoparticles deposited thereinxAnd (3) a membrane.
The fourth layer 14 is formed on the third layer 13 (S14). The fourth layer 14 is formed using, for example, a pull-out method or a convection self-assembly method. The nickel nitrate and ammonia are neutralized to produce nickel hydroxide crystallites. The generated microcrystals are deposited and laminated on the third layer 13 by a pull-out method or a convection self-assembly method. Thus, a nickel hydroxide film can be formed. Therefore, a microcrystalline nickel hydroxide layer can be formed as the fourth layer 14. A 3500nm thick nickel hydroxide layer may be formed by a convective self-assembly process.
Next, the second electrode 22 is formed on the fourth layer 14 (S15). Examples of the method of forming the second electrode 22 include vapor film deposition methods such as sputtering, ion plating, electron beam vapor deposition, vacuum deposition, and chemical vapor deposition. Note that the second electrode 22 may be partially formed using a mask. The second electrode 22 can be formed by electrolytic plating, electroless plating, or the like. As the metal used for the plating process, copper alloy, nickel, silver, gold, zinc, tin, or the like can be generally used. For example, the second electrode 22 is an Al film having a thickness of 300 nm.
By the above-described manufacturing method, the high-performance secondary battery 100 can be manufactured with high productivity. For example, the storage capacity can be increased by adding a positive electrode active material. Further, in the step of forming the fourth layer 14, the formation of microcrystals and the film formation step can be separated from each other. That is, after the formation of the crystallites, a nickel hydroxide film having hexagonal crystallites can be deposited on the third layer 13. In addition, a metal material (Co, Zn, or the like) for improving the performance can be easily added during the formation of the microcrystal. Furthermore, the electrical stimulation step can be omitted.
[ second embodiment ]
The structure of a secondary battery 100A according to the second embodiment will be described with reference to fig. 10. Fig. 10 is a sectional view showing the configuration of the secondary battery 100A. In the secondary battery 100A, the third layer 13 serving as the electrolyte layer has a two-layer structure. In particular, the third layer 13 comprises TaOxLayer 13a and TEOS layer 13 b. The construction other than the third layer 13 is the same as that of the first embodiment, and thus the description of the secondary battery according to the second embodiment is omitted.
The TEOS layer 13b is provided on the TaOxOn the layer 13 a. That is, the TEOS layer 13b is formed on the TaOxBetween the layer 13a and the second electrode 22. TEOS layer 13b and TaOxThe layer 13a is in contact with the second electrode 22. Due to TaOxLayer 13a and TaOxLayer similarity, the TaOxThe layer is the third layer 13 according to the first embodiment, so the pair of taos will be omittedxDescription of layer 13 a.
The TEOS layer 13b is formed by a chemical vapor deposition method (CVD method) using Tetraethylorthosilicate (TEOS). The film thickness of the TEOS layer 13b can be, for example, about 50nm to 200 nm.
In this configuration, the same effects as those of the first embodiment can be obtained. That is, since the nickel hydroxide layer containing hexagonal crystallites is formed as the fourth layer 14, the storage capacity can be increased.
The secondary battery may have layers other than the first to fourth layers 11 to 14 between the electrodes. That is, layers other than the above-described first layer 11 to fourth layer 14 may be added. The third layer 13 serving as the electrolyte layer may be formed of a material other than those according to the first and second embodiments.
Although examples of the embodiments of the present disclosure have been described above, the present disclosure also includes appropriate modifications that do not impair the objects and advantages of the present disclosure, and the present disclosure is not limited by the above-described embodiments.
The present application claims priority based on japanese patent application No. 2019-15088 filed on 31/1/2019, the entire disclosure of which is incorporated herein by reference.
Description of the reference numerals
100 secondary battery
11 first layer
12 second layer
13 third layer
14 fourth layer
21 first electrode
22 a second electrode.

Claims (7)

1. A secondary battery comprising:
a first electrode;
a second electrode;
a first layer disposed between the first electrode and the second electrode and including a first n-type oxide semiconductor material;
a second layer disposed on the first layer and including a second n-type oxide semiconductor material and a first insulating material;
a third layer that is provided on the second layer and is a solid electrolyte layer; and
a fourth layer disposed on the third layer and comprising hexagonal Ni (OH)2And (4) microcrystals.
2. The secondary battery according to claim 1,
in an X-ray diffraction pattern obtained by performing X-ray diffraction measurement by grazing incidence X-ray diffraction method on the fourth layer, there are shown Ni (OH)2The first peak of diffraction intensity of (001) plane of (2) and shows Ni (OH)2A second peak of the diffraction intensity of the (100) plane of (c).
3. A secondary battery comprising:
a first electrode;
a second electrode;
a first layer disposed between the first electrode and the second electrode and including a first n-type oxide semiconductor material;
a second layer disposed on the first layer and including a second n-type oxide semiconductor material and a first insulating material;
a third layer that is provided on the second layer and is a solid electrolyte layer; and
a fourth layer disposed on the third layer and comprising nickel hydroxide crystallites, wherein,
in an X-ray diffraction pattern obtained by performing X-ray diffraction measurement by grazing incidence X-ray diffraction method on the fourth layer, there are shown Ni (OH)2The first peak of diffraction intensity of (001) plane of (2) and shows Ni (OH)2A second peak of the diffraction intensity of the (100) plane of (c).
4. The secondary battery according to claim 2 or 3,
the full width at half maximum of the first peak is greater than the full width at half maximum of the second peak.
5. The secondary battery according to any one of claims 1 to 4, wherein
The crystallite has a planar size of 200nm or less.
6. The secondary battery according to any one of claims 1 to 5,
the fourth layer is in contact with the second electrode.
7. The secondary battery according to any one of claims 1 to 6,
the thickness of the fourth layer is 500nm or more.
CN202080010602.9A 2019-01-31 2020-01-30 Secondary battery Pending CN113424349A (en)

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